Catalytic halogenated hydrocarbon processing and ruthenium catalysts for use therein

ABSTRACT

Processes for decreasing the chlorine to carbon ratio for halogenated hydrocarbons containing chlorine and from 1 to 6 carbon atoms, in the presence of a catalyst are disclosed. The processes are each characterized by employing a catalyst comprising ruthenium on a support of (i) fluorided alumina, (ii) aluminum fluoride, or (iii) fluorides of Zn, Mg, Ca, Ba, Y, Sm, Eu, and/or Dy. Also disclosed are multiphase catalyst compositions of ruthenium supported on fluorides of Zn, Mg, Ca, Ba, Y, Sm, Eu and/or Dy.

This application is a national filing under 35 USC 371 of InternationalApplication No. PCT/US96/18952 filed Nov. 26, 1996 claiming priority ofU.S. Provisional application Ser. No. 60/007,702 filed Nov. 29, 1995.

FIELD OF THE INVENTION

This invention relates to supported ruthenium compositions and theiruse, and more particularly to supported ruthenium catalysts and theiruse for processing halogenated hydrocarbons.

BACKGROUND

A variety of metal catalysts have been proposed for use in processes fordimerizing chlorine-containing fluorocarbons, for dehalogenatinghalogenated fluorocarbons for hydrogenolyzing halogenated hydrocarbonsand for hydrofluorating halogenated hydrocarbons (see e.g., PCTPublication No. WO 95/05353 for dimerization examples and L. E. Manzeret al., Adv. Catal. (39) pp. 329-350 (1993) for examples of the otherlisted processes). The products of these processes are useful for thepreparation of hydrofluorocarbons which can be substituted forchlorofluorocarbons and hydrochlorofluorocarbons which have been used asrefrigerants, blowing agents and cleaning agents. Some of the olefinicproducts are useful as monomers for fluoropolymers. There is an interestin developing economical processes for the preparation of suchcompounds.

SUMMARY OF THE INVENTION

This invention provides processes for decreasing the chlorine to carbonratio for halogenated hydrocarbons containing chlorine and from 1 to 6carbon atoms, in the presence of a catalyst. The processes are eachcharacterized by employing a catalyst comprising ruthenium on a supportselected from the group consisting of (i) fluorided alumina, (ii)aluminum fluoride, and (iii) fluorides of at least one metal selectedfrom the group consisting of Zn, Mg, Ca, Ba, Y, Sm, Eu, and Dy (e.g.,zinc fluoride, magnesium fluoride, calcium fluoride, barium fluoride,yttrium fluoride, samarium fluoride, europium fluoride and/or dysprosiumfluoride).

This invention further provides multiphase catalyst compositionsconsisting essentially of ruthenium supported on fluorides of at leastone element selected from the group consisting of Zn, Mg, Ca, Ba, Y, Sm,Eu and Dy.

DETAILED DESCRIPTION

The catalytic processes of this invention include processes fordimerizing, processes for dehalogenating, processes for hydrogenolyzing,and processes for increasing the fluorine content of chlorinatedfluorocarbons (i.e., compounds containing only carbon, chlorine andfluorine) and chlorinated hydrofluorocarbons (i.e., compounds containingonly carbon, hydrogen, chlorine and fluorine). The chlorinatedfluorocarbons and chlorinated hydrofluorocarbons can contain from 1 to 6carbon atoms. The processes employ a supported ruthenium catalyst. Thesupport (i.e., carrier) can be fluorided alumina, aluminum fluoride,zinc fluoride, magnesium fluoride, calcium fluoride, barium fluoride,yttrium fluoride, samarium fluoride, europium fluoride and/or dysprosiumfluoride, Fluorided alumina and aluminum fluoride can be prepared asdescribed in U.S. Pat. No. 4,902,838. The other metal fluorides as wellas aluminum fluoride can be obtained commercially. The ruthenium can besupported on the carrier by techniques well known in the art such asimpregnation. The concentration of ruthenium on the support is typicallyin the range from about 0.01 to 30 weight percent, and is preferablyfrom about 0.5 to 20 weight percent.

Included in this invention is a process for dimerizing saturatedcompounds having the formula C_(n) H_(a) Cl_(b) F_(c) where n is aninteger from 1 to 4, a is an integer from 0 to 1, b is an integer from 2to 9, c is an integer from 0 to 9, where a+b+c equals 2n+2, and wheretwo chlorines that are removed are on the same carbon atom, by reactingsaid compound with hydrogen in the vapor phase to produce olefins of theformula C_(2n) H_(2a) Cl_(2b-4) F_(2c) ; a process for dehalogenating asaturated compound having the formula C_(m) H_(d) Cl_(e) F_(f) where mis an integer from 2 to 6, d is an integer from 0 to 2, e is an integerfrom 2 to 4, f is an integer from 3 to 12, where d+e+f equals 2m+2, byreacting said compound with hydrogen in the vapor phase to produceolefins of the formula C_(m) H_(d) Cl_(e-y) F_(f-y), where y is aninteger from 1 to 2 when m is an integer from 2 to 3, and y is aninteger from 2 to 4 when m is an integer from 4 to 6, provided that achlorine atom on each of two adjacent carbons or a fluorine and achlorine atom on two adjacent carbons (but not a fluorine atom on eachof two adjacent carbons) are removed; a process for increasing thefluorine content of a saturated or olefinic compound having the formulaC_(k) H_(g) Cl_(h) F_(i) where k is an integer from 1 to 6, g is aninteger from 0 to 4, h is an integer from 1 to 13, i is an integer from0 to 13, provided that h is at least 1 when the compound is saturated,by reacting said compound with HF in the vapor phase; and a process forthe hydrogenolysis of a compound of the formula CF₃ (CF₂)_(p) CCl₂(CF₂)_(q) CF₃ where p and q are independently 0 or 1, by reacting saidcompound with hydrogen in the vapor phase.

The dimerization reaction of said compounds of the formula C_(n) H_(a)Cl_(b) F_(c) with hydrogen is typically conducted at a temperature fromabout 100° C. to 400° C., preferably from about 125° C. to 375° C., andmore preferably from about 150° C. to about 300° C. Typically, thecontact time is from about 1 to about 100 seconds, preferably from about5 to about 60 seconds. The mole ratio of hydrogen to C_(n) H_(a) Cl_(b)F_(c) compound(s) ordinarily should be at least about 0.25:1. Typically,the molar ratio of hydrogen to said compounds of the formula C_(n) H_(a)Cl_(b) F_(c) ranges from about 0.5:1 to about 10:1, and is preferablyabout 0.5:1 to 5:1, and more preferably about 0.5:1 to 2:1. In general,with a given catalyst composition, the higher the temperature and thelonger the contact time, the greater is the conversion to dimerizedproducts. The above variables can be balanced, one against the other, sothat the formation of dimerized products is maximized.

Examples of halogenated hydrocarbons of the formula C_(n) H_(a) Cl_(b)F_(c) which may be reacted with hydrogen include, CCl₄, CCl₃ CClF₂, CCl₃CF₃, CF₃ CCl₂ CF₃, CCl₃ CF₂ CF₃, CCl₃ CF₂ CF₂ CF₃ and CF₃ CCl₂ CF₂ CF₃.Of note is a catalytic process for producing cis and trans2,3-dichloro-1,1,1,4,4,4-hexafluorobutene-2 (i.e., F1316mxx or CF₃CCl═CClCF₃) by the reaction of hydrogen with CCl₃ CF₃. This dimerizationreaction is done in the presence of the supported ruthenium catalystsdescribed above and is preferably conducted at about 125° C. to 300° C.,more preferably about 150° C. to 250° C.

Also of note is a catalytic process for producing cis and trans3,4-dichloro-1,1,1,2,2,5,5,6,6,6-decafluorohexene-3 (i.e., F151-10mcxxor C₂ F₅ CCl═CClC₂ F₅). Starting materials include1,1,1-trichloro-2,2,3,3,3-pentafluoropropane. A catalytic process forproducing 2,3-trifluoromethyl-1,1,1,4,4,4-hexafluorbutene-2 (i.e.,F151-12mmtt or (CF₃)₂ C═C(CF₃)₂ from2,2-dichloro-1,1,1,3,3,3-hexafluoropropane is also of note.

The dimerized products which are unsaturated and/or contain chlorine canbe further reacted with hydrogen or a fluorinating agent (e.g., HF) inthe presence of the same or optionally a second catalyst. Furtherreacting the dimerized products with hydrogen (optionally using a secondcatalyst) can produce hydrofluorocarbons. Reaction with a fluorinatingagent can produce a hydrofluorocarbon or a perfluorinated alkane.

The catalyst used for the hydrogenation reaction may be the samecatalyst used for the dimerization reaction or may be selected frommetals known to provide significant hydrogenolysis activity on supportssuch as alumina, fluorided alumina and carbon. A preferred catalystcontains at least one metal selected from the group consisting ofrhenium, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridiumand platinum supported on carbon with an ash content of less than 0.5%by weight. The reaction of the dimerized products and hydrogen can beperformed in liquid or vapor-phase using well-known chemical engineeringpractice, which includes continuous, semi-continuous or batchoperations. The hydrogenolysis process is achieved at atmospheric orsuperatmospheric pressures.

The fluorinating agent may be chosen from the group consisting ofhydrogen fluoride, cobalt fluoride, elemental fluorine or fluoridesalts. Any of the known art catalysts and conditions may be used for thehydrofluorination in either the vapor phase (e.g., chromium oxide) orthe liquid phase (e.g., antimony chloride).

The dehalogenation reaction of said compounds of the formula C_(m) H_(d)Cl_(e) F_(f) with hydrogen is typically conducted at a temperature fromabout 100° C. to 350° C., preferably from about 125° C. to 325° C., andmore preferably from about 150° C. to about 300° C. Typically, thecontact time is from about 1 to about 100 seconds, preferably from about5 to about 60 seconds. The molar ratio of hydrogen to C_(m) H_(d) Cl_(e)F_(f) compound(s) ordinarily should be at least about 1:1. Typically,the molar ratio of hydrogen to said compounds of the formula C_(m) H_(d)Cl_(e) F_(f) ranges from about 1:1 to about 5:1, preferably about 1:1 to3:1, and more preferably about 1:1 to 2:1. In general, with a givencatalyst composition, the higher the temperature and the longer thecontact time, the greater is the conversion to dehalogenated products.The above variables can be balanced, one against the other, so that theformation of dehalogenated products is maximized.

Examples of halogenated hydrocarbons of the formula C_(m) H_(d) Cl_(e)F_(f) which may be reacted with hydrogen include CCl₃ CClF₂, CCl₂FCClF₂, CClF₂ CCl₂ CF₃, CF₃ CCl₂ CF₃, CClF₂ CClFCClF₂, CClF₂ CF₂ CClF₂,CClF₂ CClFCF₃ and CCl₂ FCF₂ CF₃. Of note is a catalytic process forproducing 2-chloro-1,1,3,3,3-pentafluoropropene-1 (i.e., F1215xc or CF₂═CCClF₃) by the reaction of hydrogen with CF₃ CCl₂ CF₃. Thisdehalogenation reaction is done in the presence of the supportedruthenium catalysts described above and is preferably conducted at about125° C. to 325° C., more preferably about 150° C. to 275° C.

Also of note is a catalytic process for producing1,1-dichloro-2,2-difluoroethene (i.e., F1112a or CF₂ ═CCl₂). Thestarting material is 1,1,1,2-tetrachloro-2,2-difluoroethane.

The hydrofluorination reaction of said compounds of the formula C_(k)H_(g) Cl_(h) F_(i) with HF is typically conducted at a temperature offrom about 150° C. to 400° C., preferably at from about 150° C. to 375°C., and more preferably at about 175° C. to about 350° C. Typically, thecontact time is from about 1 to about 120 seconds, preferably from about5 to about 60 seconds. The amount of HF ordinarily should be at least astoichiometric amount. Typically, the molar ratio of HF to saidcompounds of the formula C_(k) H_(g) Cl_(h) F_(i) ranges from about 1:1to about 20:1, preferably from about 2:1 to 10:1, and more preferablyfrom about 3:1 to 6:1. In general, with a given catalyst composition,the higher the temperature and the longer the contact time, the greateris the conversion to fluorinated products. The above variables can bebalanced, one against the other, so that the formation of higherfluorine substituted products is maximized.

An example of a saturated compound which may be reacted with HF includesCCl₃ CF₃. Of note is a catalytic process for producing2,2-dichloro-1,1,1,2-tetrafluoroethane (CCl₂ FCF₃, i.e., CFC-114a) bythe fluorination of CCl₃ CF₃.

The hydrogenolysis reaction of said compounds of the formula CF₃(CF₂)_(p) CCl₂ (CF₂)_(q) CF₃ with H₂ is typically conducted at atemperature of from about 100° C. to 350° C., preferably of from about150° C. to 275° C., more preferably from about 150° C. to 250° C.Typically, the contact time is from about 1 to about 100 seconds,preferably from about 5 to about 60 seconds. Typically, the molar ratioof hydrogen to said compounds of the formula CF₃ (CF₂)_(p) CCl₂(CF₂)_(q) CF₃ ranges from about 0.5:1 to 10:1 and is preferably fromabout 1:1 to 4:1. Of note is the monohydrogenolysis of CF₃ CCl₂ CF₃ toCF₃ CHClCF₃ using ruthenium supported on barium fluoride.

The processes for dimerizing, dehalogenating, hydrofluorinating, andhydrogenolyzing halogenated hydrocarbons in accordance with thisinvention may be conducted in any suitable reactor, including fixed andfluidized bed reactors. The reaction vessel should be constructed frommaterials which are resistant to the corrosive effects of hydrogenfluoride and hydrogen chloride such as Inconel™ nickel alloy andHastelloy™ nickel alloy.

Atmospheric and superatmospheric pressures are the most convenient andare therefore the preferred method of operation. The reaction productsmay be separated by conventional techniques such as distillation. It isnoted that many halogenated hydrocarbon products of the above reactionsform azeotropes with HF, HCl, or other halogenated hydrocarbons.

Examples of catalysts of this invention include ruthenium supported onzinc fluoride, magnesium fluoride, calcium fluoride, barium fluoride,yttrium fluoride, samarium fluoride, europium fluoride, or dysprosiumfluoride. Also included are catalysts of ruthenium supported onfluorides of two or more metals selected from the group consisting ofZn, Mg, Ca, Ba, Y, Sm, Eu and Dy. Examples of such combined fluoridesinclude calcium-magnesium fluoride where the atomic ratio of calcium tomagnesium is between about 1:1 and 4:1; and calcium-barium fluoridewhere the atomic ratio of calcium to barium is between about 1:1 and4:1. Typically, the ruthenium is from about 0.1 to 30 weight percent ofthe catalyst. Of note are compounds where the ruthenium is from about0.5 to 20 weight percent of the catalyst.

Without further elaboration, it is believed that one skilled in the artcan, using the description herein, utilize the present invention to itsfullest extent. The following preferred specific embodiments are,therefore, to be construed as merely illustrative, and does notconstrain the remainder of the disclosure in any way whatsoever.

EXAMPLES Ruthenium on Metal Fluoride Catalyst Preparation Procedure

Ruthenium Trichloride (RuCl₃.xH₂ O) was dissolved in distilled water andadded to a plastic beaker containing the metal fluoride. The weights ofthe ruthenium trichloride and the metal fluorides were selected toprovide a catalyst containing 2 wt. % Ru on the support (see table). Theslurry was kept at room temperature with occasional stirring for about 2hours. The slurry was then dried at 110° C. to 120° C. overnight.

    ______________________________________    Support (wt.) g                  RuCl.sub.3 (wt.) g                            % Ru in RuCl.sub.3.xH.sub.2 O    ______________________________________    CaF.sub.2 (200.0)                  9.52      42    MgF.sub.2 (200.0)                  11.29     35    ZnF.sub.2 (47.5)                  2.68      35    YF.sub.3 (80.0)                  3.80      42    AlF.sub.3 .3H.sub.2 O (100.0)                  3.47      41    BaF.sub.2 (100.0)                  4.80      41    DyF.sub.3 (100.0)                  4.80      41    EuF.sub.3 (48.0)                  2.30      41    SmF.sub.3 (75.0)                  3.60      41    ______________________________________

5% Ru on Fluorided Alumina Catalyst Preparation

A commercially available sample of 5.0 weight percent ruthenium onalumina (12.22 g, 12/20 mesh (1.68 mm to 0.84 mm) granules) was placedin a reactor and heated to 175° C. in a flow of nitrogen (20 cc/min.)for about 2 hours. At the end of this period the nitrogen flow wasincreased to 50 cc/min. and an HF flow (50 cc/min.) was passed throughthe reactor. After the initial exotherm subsided (about three hours),the nitrogen flow was reduced to 20 cc/min. and the HF flow increased to80 cc/min. The reactor temperature was then gradually increased to about400° C. over about a five hour period and maintained at 400° C. for anadditional 30 minutes. The HF flow was then stopped and the reactorpurged with nitrogen and cooled to about 150° C. The catalyst was thentreated with hydrogen (22 cc/min) at this temperature for about 0.5hours followed by treatment with hydrogen (22 cc/min) for about another0.5 hours at 175° C. before use.

General Procedure for Catalyst Evaluation

For the examples using metal fluoride as the support, the granulatedcatalyst (12/20 mesh, 1.68 mm to 0.84 mm) was placed in a 1/2" (1.27 cm)Inconel™ nickel alloy reactor heated in a fluidized sand bath. Thecatalyst was heated to about 200° C. in a flow of nitrogen (50 cc/min)for about two hours. After this period, it was heated in a stream ofhydrogen (50 cc/min) for about 2 hours at about 200° C. prior toevaluation. Liquid feeds were delivered using a metering pump and werevaporized and mixed with either HF or hydrogen prior to entering thereactor. Vapor feeds were delivered using standard mass flow meters.

General Procedure for Product Analysis

The following general procedure is illustrative of the analytical methodused. Part of the total reactor effluent was sampled on-line for organicproduct analysis using a Hewlett Packard HP 5890 gas chromatographequipped with a 20' (6.1 m) long×1/8" (0.32 cm) diameter tubingcontaining Krytox™ perfluorinated polyether on an inert carbon support.The helium flow was 35 cc/min. Gas chromatographic conditions were 70°C. for an initial hold period of three minutes followed by temperatureprogramming to 180° C. at a rate of 6° C./minute. Positive productidentification including determination of molecular formulas ofcompounds of undetermined structure was obtained using massspectroscopy.

The bulk of the reactor effluent containing organic products and alsoinorganic acids such as HCl and HF was treated with aqueous caustic toneutralize the acids prior to disposal.

    ______________________________________    Legend    ______________________________________    F11 is CFCl.sub.3    F112a is CF.sub.2 ClCCl.sub.3    F113 is CF.sub.2 ClCFCl.sub.2                         F113a is CF.sub.3 CCl.sub.3    F114a is CF.sub.3 CFCl.sub.2                         F115 is CF.sub.3 CF.sub.2 Cl    F122 is CHCl.sub.2 CClF.sub.2                         F123 is CF.sub.3 CHCl.sub.2    F124 is CF.sub.3 CFHCl                         F133a is CF.sub.3 CH.sub.2 Cl    F134a is CF.sub.3 CH.sub.2 F                         F142b is CH.sub.3 CClF.sub.2    F143a is CH.sub.3 CF.sub.3                         F215aa is CF.sub.2 ClCCl.sub.2 CF.sub.3    F215cb is CCl.sub.3 CF.sub.2 CF.sub.3                         F225ca is CF.sub.3 CF.sub.2 CHCl.sub.2    F216aa is CF.sub.3 CCl.sub.2 CF.sub.3                         F216ba is CF.sub.2 ClCFClCF.sub.3    F217ba is CF.sub.3 CClFCF.sub.3                         F226da is CF.sub.3 CClHCF.sub.3    F236fa is CF.sub.3 CH.sub.2 CF.sub.3                         F245cb is CH.sub.3 CF.sub.2 CF.sub.3    F356mff is CF.sub.3 CH.sub.2 CH2CF.sub.3                         HFP is CF.sub.3 CF═CF.sub.2    TCE is CHCl═CCl.sub.2                         PCE is CCl.sub.2 ═CCl.sub.2    F1111 is C3Cl.sub.5 F                         F1112a is CF.sub.2 ═CCl.sub.2    F1132a is CF.sub.2 ═CH.sub.2                         1213xa is CF.sub.3 CCl═CCl.sub.2    F1214 is C3Cl.sub.2 F.sub.4                         F1215xc is CF.sub.3 CCl═CF.sub.2    F1216 is CF.sub.3 CF═CF.sub.2                         F1223 is C.sub.3 HCl.sub.2 F.sub.3    F1224 is C.sub.3 HClF.sub.4                         F1225zc is CF.sub.3 CH═CF.sub.2    F1326 is C.sub.4 HClF.sub.6    F1314 is cis/trans isomers of CF.sub.2 ClCCl═CClCF.sub.2 Cl    F318 is isomers of C.sub.4 Cl.sub.2 F.sub.8    F1316mxx is CF.sub.3 CCl═CClCF.sub.3 (cis/trans isomers)    F1318 is cis/trans isomers of CF.sub.3 CF═CFCF.sub.3    F151-10mcxx is C.sub.2 F.sub.5 CCl═CClC.sub.2 F.sub.5 (cis/trans    isomers)    F151-12mmtt is (CF.sub.3).sub.2 C═C(CF.sub.3).sub.2    ______________________________________

Example 1 Reaction of F113a and Hydrogen Catalyst: 5% Ru/FluoridedAlumina (12.22 g, 15 mL)

The catalyst was fluorided in the reactor prior to use according to theprocedure described above. The H₂ :F113a molar ratio was varied between0.5:1 to 2.0:1 and the contact time was 20 seconds for all runs. Resultsin area % at various temperatures are shown in the table.

    __________________________________________________________________________    Temp.        Ratio    ° C.        H.sub.2 :F113a             F143a                 F114a                     F123                         F113a                             t-F1316mxx                                   c-F1316mxx                                         Others    __________________________________________________________________________    175 0.5  6.1 0.6 1.7 62.2                             19.5  9.4   0.7    175 1.0  16.3                 0.6 4.1 36.3                             27.9  13.4  1.5    175 2.0  29.7                 0.6 6.9 15.0                             30.7  14.4  2.8    200 0.5  3.9 0.6 1.2 59.9                             22.2  11.6  0.7    290 1.0  11.6                 0.6 4.0 27.0                             36.6  18.9  1.4    200 2.0  20.1                 0.6 6.5 7.2 41.9  21.3  2.4    225 2.0  16.3                 0.7 6.9 1.0 46.1  26.0  3.2    __________________________________________________________________________

Others include F1132a, F142b, F1112a, F133a, F113 and small quantitiesof unidentified products.

    ______________________________________    Selectivity calculation for the above table    Temp.          Conv.   % Sel. to  Combined Sel. to    ° C.          H.sub.2 :F113a                   %       F143a F1316mxx                                        F143a + F1316mxx    ______________________________________    175   0.5      37.8    16.1  76.6   92.7    175   1.0      63.7    25.6  64.8   90.4    175   2.0      85.0    34.9  53.0   87.9    200   0.5      40.1    9.7   84.3   94.0    200   1.0      73.0    15.9  76.0   91.9    200   2.0      92.8    21.7  68.1   89.8    225   2.0      99.0    16.4  72.8   89.2    ______________________________________

Example 2 Reaction of F216aa and Hydrogen Catalyst: 5% Ru/FluoridedAlumina (12.22 g 15 mL)

The catalyst was the same as that used in Example 1. The H₂ :F216aamolar ratio was varied between 0.5:1 to 1.0:1 and the contact time was20 seconds for all runs. Results in area % at various temperatures areshown in the table.

    __________________________________________________________________________    Temp.        Ratio                     F151-    ° C.        H.sub.2 :F216aa             F236fa                 F1215xc                      F226da                          F216aa                              F216ba                                  12mmtt                                      Others    __________________________________________________________________________    200 1.0  3.7 1.1  14.4                          66.3                              1.1 12.8                                      0.6    200 0.5  2.2 0.7  8.5 76.3                              1.1 10.8                                      0.4    250 0.5  3.2 1.6  10.0                          59.3                              1.1 24.2                                      0.6    300 0.5  0.9 0.8  7.0 55.9                              1.1 32.0                                      2.4    300 1.0  2.3 2.4  16.7                          24.3                              1.2 50.7                                      2.5    __________________________________________________________________________

Others include F1216, 1225zc, and unidentified products.

    ______________________________________    Selectivity data for the above table            % Sel. to    % F216aa Conv.              F226da  F151-12mmtt                                 F226da + F151-12mmtt    ______________________________________    33.7      42.7    38.0       80.7    23.7      35.9    45.6       81.5    40.7      24.5    59.4       83.9    44.1      15.9    72.6       88.5    75.7      22.1    67.0       89.1    ______________________________________

Example 3 Reaction of F216aa and Hydrogen Catalyst: 2% Ru/AlF₃, 8.7 g,10 mL

The H₂ :F216aa molar ratio was varied between 0.5:1 to 1.0:1 and thecontact time was 20 seconds for all runs. Results in area % at varioustemperatures are shown in the table.

    __________________________________________________________________________    Temp.        Ratio    ° C.        H.sub.2 :F216aa             F236fa                 F1215xc                      F226da                          F216aa                              F51-12mmtt                                    F1213xa                                         Others    __________________________________________________________________________    175 1.0  5.0 3.5  5.3 76.6                              8.1   0.0  1.6    200 1.0  6.3 5.4  7.4 63.4                              15.3  0.0  2.2    200 0.5  3.3 3.1  4.3 74.7                              13.4  0.0  1.2    250 0.5  2.3 3.4  7.2 57.0                              29.0  0.0  1.1    300 0.5  0.7 0.2  7.6 58.5                              28.5  2.8  1.8    300 1.0  2.3 1.7  21.6                          19.6                              47.2  3.1  4.5    __________________________________________________________________________

Others include CH₄, F1225zc, F217ba, C₆ F₁₀, C₆ HF₁₁, F1223, TCE and C₆H₂ F₁₂.

Example 4 Reaction of F113a and Hydrogen Catalyst: 2% Ru/AlF₃, 8.7 g, 10mL

The H₂ :F113a molar ratio was varied between 0.5:1 to 1.0:1 and thecontact time was 20 seconds for all runs. Results in area % at varioustemperatures are shown in the table.

    __________________________________________________________________________    Temp.        Ratio    ° C.        H.sub.2 :F113a             F143a                 F114a                     F1112a                         F123                            F113                               F113a                                   t-F1316                                       c-F1316                                           Others    __________________________________________________________________________    175 1.0  1.8 0.7 0.7 2.6                            0.3                               32.4                                   39.3                                       21.9                                           0.3    175 2.0  3.3 0.8 0.8 2.7                            0.3                               20.2                                   45.9                                       25.5                                           0.5    175 0.5  0.6 0.5 0.4 1.1                            0.3                               59.5                                   23.9                                       13.7                                           0.1    200 0.5  0.7 0.7 0.4 1.1                            0.3                               53.6                                   26.8                                       16.4                                           0.2    200 1.0  1.5 0.9 0.9 2.2                            0.3                               27.2                                   41.4                                       25.0                                           0.4    __________________________________________________________________________

Example 5 Reaction of F113a/CCl₄ (1:1) and Hydrogen Catalyst: 2%Ru/AlF₃, 8.7 g, 10 mL

The H₂ : F113a:CCl₄ ! molar ratio was varied between 1:1 to 2:1 and thecontact time was 20 seconds for all runs. Results in area % at varioustemperatures are shown in the next two tables.

    __________________________________________________________________________    Temp.        Ratio    ° C.        H.sub.2 : 113a:CCl.sub.4 !               CH.sub.4                  C.sub.2 H.sub.6                     F143a                         F12                            F114a                                F11                                   F1112a                                       F123                                          CHCl.sub.3    __________________________________________________________________________    175 1      0.1                  0.0                     0.0 0.0                            0.1 0.2                                   0.4 0.2                                          1.4    175 2      0.3                  0.1                     0.1 0.0                            0.1 0.2                                   0.6 0.3                                          1.2    200 2      0.7                  0.2                     0.4 0.0                            0.4 0.2                                   1.6 1.4                                          0.5    250 2      2.9                  0.8                     2.4 0.3                            2.4 0.2                                   7.7 6.0                                          0.0    250 1      1.0                  0.1                     0.1 0.6                            0.5 1.2                                   11.1                                       1.3                                          0.9    __________________________________________________________________________    Temp.    ° C.        F113           F113a               CCl4                  F1111                      t-F1316                          c-F1316                              F1213xa                                   PCE                                      C.sub.4 Cl.sub.6                                          Others    __________________________________________________________________________    175 0.2           65.1               0.5                  0.0 0.5 0.3 3.9  26.8                                      0.0 0.3    175 0.2           62.3               0.2                  0.0 0.8 0.5 3.8  28.9                                      0.0 0.4    200 0.2           47.1               0.2                  0.0 7.1 4.6 4.8  29.7                                      0.0 0.9    250 0.3            5.1               0.0                  0.3 21.9                          15.0                              7.9  21.6                                      2.3 3.1    250 0.2           53.7               0.4                  0.4 2.7 1.9 3.6  16.4                                      1.6 2.2    __________________________________________________________________________

Example 6 Reaction of F113a and Hydrogen Catalyst: 2% Ru/ZnF₂, 16.4 g,10 mL

The H₂ :F113a molar ratio was varied between 0.5:1 to 2:1 and thecontact time was 20 seconds for all runs. Results in area % at varioustemperatures are shown in the table.

    __________________________________________________________________________    Temp.        Ratio    ° C.        H.sub.2 :F113a             F143a                 F114a                     F123                        F113                           F113a                               t-F1316                                   c-F1316                                       Others    __________________________________________________________________________    175 1.0  0.6 0.2 1.0                        0.3                           47.2                               33.4                                   16.9                                       0.4    175 2.0  1.5 0.2 1.4                        0.3                           31.2                               43.6                                   21.4                                       0.4    200 2.0  2.2 0.3 2.4                        0.4                           9.0 54.7                                   30.2                                       0.9    200 1.0  0.8 0.3 1.9                        0.4                           22.7                               46.5                                   26.9                                       0.5    200 0.5  0.2 0.2 0.8                        0.3                           51.7                               29.0                                   17.5                                       0.2    __________________________________________________________________________

Example 7 Reaction of F216aa and Hydrogen Catalyst: 2% Ru/ZnF₂, 16.4 g,10 mL

The H₂ :F216aa molar ratio was varied between 0.5:1 to 2:1 and thecontact time was 20 seconds for all runs. Results in area % at varioustemperatures are shown in the table.

    __________________________________________________________________________    Temp.        Ratio    ° C.        H.sub.2 :F216aa             F1225zc                  F236fa                      F1215xc                           F226da                               F216aa                                   F151-12mtt                                         Others    __________________________________________________________________________    200 1.0  0.0  0.2 0.0  0.7 84.3                                   14.4  0.3    250 1.0  0.1  0.4 0.2  3.7 42.7                                   50.1  2.7    250 0.5  0.0  0.1 0.1  2.5 69.0                                   25.4  2.8    300 0.5  0.2  0.2 1.3  3.3 71.3                                   14.1  9.7    300 1.0  0.3  0.3 1.7  4.0 73.9                                   6.6   13.3    __________________________________________________________________________

Example 8 Reaction of F113a and Hydrogen Catalyst: 2% Ru/MgF₂, 13.5 g,15 mL

The H₂ :F114a molar ratio was varied between 1:1 and 4:1, the contacttime was 20 seconds and the temperature was 175° C. for all runs.Results in area % are shown in the table.

    __________________________________________________________________________    Ratio    H.sub.2 :F113a         F143a             F114a                 F123                    F113a                        t-F1316mxx                              c-F1316mxx                                    Others    __________________________________________________________________________    1    2.5 0.8 3.1                    33.3                        40.0  19.6  0.8    1    2.4 0.7 2.8                    33.5                        40.1  19.8  0.7    1    2.2 0.7 2.6                    34.8                        39.4  19.5  0.7    2    5.2 0.7 3.6                    18.3                        48.0  23.3  0.9    4    10.5             0.8 4.5                    7.4 51.2  24.3  1.3    __________________________________________________________________________

Example 9 Reaction of F216aa and Hydrogen Catalyst: 2% Ru/MgF₂, 13.5 g,15 mL

The H₂ :F216aa molar ratio was varied between 1:1 and 2:1 and thecontact time was 20 seconds. Results in area % at various temperaturesare shown in the table.

    __________________________________________________________________________    Temp.        Ratio    ° C.        H.sub.2 :F216aa             F1225zc                  F236fa                      F1215xc                           F226da                               F216aa                                   F151-12mmtt                                          Others    __________________________________________________________________________    175 1    0.2  2.8 9.8  3.8 77.6                                   5.1    0.7    175 2    0.3  4.6 13.8 4.7 70.1                                   5.8    0.8    200 1    0.3  3.1 20.9 4.4 62.2                                   8.1    0.9    250 1    0.9  4.0 54.7 8.4 20.1                                   10.8   1.1    300 1    0.6  2.4 67.9 10.1                               5.0.                                   11.4   2.7    300 2    2.0  4.3 65.3 11.2                               0.0 13.3   3.9    __________________________________________________________________________

Example 10 Reaction of F215cb and Hydrogen Catalyst: 2% Ru/MgF₂, 13.5 g,15 mL

The H₂ :F215cb molar ratio was varied between 1:1 and 2:1 and thecontact time was 20 seconds. The feed was 95.3% 215cb, 2.3% CCl₄ andsmall amounts of other products. Results in area % at 150° C. are shownin the table.

    __________________________________________________________________________    Temp.        Ratio    ° C.        H.sub.2 :215cb             F215cb                 PCE                    F151-10mcxx                           C.sub.4 F.sub.5 Cl.sub.3                               F151-10mcxx                                      Others    __________________________________________________________________________    150 2    17.8                 3.1                    68.9   NA  6.7    3.5    150 1    44.1                 3.1                    31.1   15.3                               2.9    3.4    __________________________________________________________________________

Others include 225ca, 245cb, and small amounts of unidentified products.NA means not analyzed.

Example 11 Reaction of F215cb and Hydrogen Catalyst: 2% Ru/CaF₂, 10.5 g,10 mL

The H₂ :F215cb molar ratio was varied between 1:1 and 2:1 and thecontact time was 20 seconds. The feed material contained 95.3% F215cb,2.3% CCl₄ and small amounts of other products. Results in area % atvarious temperatures are shown in the table.

    __________________________________________________________________________    Temp.        Ratio    ° C.        H.sub.2 :215cb             F215aa                 F215cb                     PCE                        F151-10mcxx                               C.sub.4 F.sub.5 Cl.sub.3                                   F151-10mcxx    __________________________________________________________________________    150 1    1.5 38.6                     3.3                        37.1   11.2                                   5.4    150 2    1.2 27.8                     3.4                        46.2   10.5                                   6.6    175 1    1.3 28.2                     3.9                        46.7   9.6 6.7    200 1    0.8 17.5                     4.0                        55.4   8.2 9.1    225 1    0.7 15.9                     3.8                        53.7   10.3                                   9.8    __________________________________________________________________________

Small amounts of other products were present.

Example 12 Reaction of F113a and Hydrogen Catalyst: 2% Ru/CaF₂, 10.5 g,10 mL

The H₂ : F113a molar ratio was varied between 1:1 and 4:1, the reactiontemperature was 175° C. and the contact time was 20 seconds. Results inarea % are shown in the table.

    __________________________________________________________________________    Ratio    H.sub.2 :F113a         F143a             F114a                 F123                    F113a                        t-F1316mxx                              c-F1316mxx                                    Others    __________________________________________________________________________    1    3.1 0.6 1.4                    63.3                        17.7  13.4  0.5    2    5.6 0.6 2.0                    51.1                        23.6  16.6  0.7    4    8.9 0.6 2.7                    39.4                        29.0  18.3  1.1    __________________________________________________________________________

Others include CH₄, F142b, F1132a, F1326, and F113.

Example 13 Reaction of F216aa and Hydrogen Catalyst: 2% Ru/CaF₂, 10.5 g,10 mL

The H₂ :F216aa molar ratio was varied between 1:1 and 2:1 and thecontact time was 20 seconds. Results in area % at various temperaturesare shown in the table.

    __________________________________________________________________________    Temp.        Ratio    ° C.        H.sub.2 :F216aa             F1225zc                  F236fa                      F1215xc                           F226da                               F216aa                                   F151-12mmtt                                          Others    __________________________________________________________________________    175 1    0.0  0.7 0.3  0.5 94.5                                   4.0    0.1    200 1    0.1  1.4 0.7  1.2 87.6                                   8.9    0.1    225 1    0.1  1.8 1.3  2.6 77.5                                   16.3   0.3    250 1    0.2  2.1 2.6  5.4 62.3                                   26.7   0.7    275 1    0.6  2.3 4.9  11.5                               41.8                                   37.9   1.1    275 2    0.8  3.6 6.8  14.9                               26.5                                   45.7   1.7    300 1    0.8  1.9 7.1  17.8                               26.5                                   44.3   1.6    __________________________________________________________________________

Example 14 Reaction of F113a and Hydrogen Catalyst: 2% Ru/BaF₂, 24.4 g,10 mL

The H₂ :113a molar ratio was 1 and the contact time was 20 seconds.Results in area % at 175° C. showed the presence of the followingcompounds: F143a, 2.0; F114a, 0.3; F123, 7.0; F1326, 0.4; F113a, 26.5;t-F1316, 41.4; c-F1316, 21.5 and 0.9 others. Others include F1132a andF113.

Example 15 Reaction of F216aa and Hydrogen Catalyst: 2% Ru/BaF₂, 24.4 g,10 mL

The H₂ :F216aa molar ratio was varied between 0.5:1 and 1:1 and thecontact time was 20 seconds. Results in area % at various temperaturesare shown in the table.

    __________________________________________________________________________    Temp.        Ratio    ° C.        H.sub.2 :F216aa             F236fa                 F1215xc                      F226da                          F216aa                              C.sub.6 F.sub.10                                 F151-12mmtt                                        Others    __________________________________________________________________________    200 1.0  0.6 40.0 33.3                          23.7                              0.7                                 1.3    0.4    200 0.5  0.4 27.6 19.2                          50.6                              0.7                                 1.2    0.3    250 0.5  0.4 35.8 6.7 53.3                              1.2                                 2.3    0.3    __________________________________________________________________________

Others include F1225zc and C₆ HF₁₁.

Example 16 Reaction of F216aa and Hydrogen Catalyst: 2% Ru/YF₃, 16.5 g,10 mL

The H₂ :F216aa molar ratio was varied between 0.5:1 and 1:1 and thecontact time was 20 seconds. Results in area % at various temperaturesare shown in the table.

    __________________________________________________________________________    Temp.        Ratio    ° C.        H.sub.2 :F216aa             F236fa                 F1215xc                      F226da                          F216aa                              C.sub.6 F.sub.10                                 C.sub.6 F.sub.12                                    Others    __________________________________________________________________________    175 1.0  2.4 19.1 7.1 64.7                              1.4                                 4.4                                    0.9    175 0.5  1.5 10.0 4.1 78.5                              1.1                                 4.2                                    0.6    200 0.5  1.8 13.7 4.3 69.9                              2.0                                 7.4                                    0.9    250 0.5  0.4 2.5  4.3 64.2                              0.3                                 27.0                                    1.4    250 1.0  0.6 3.7  6.2 52.8                              0.3                                 35.6                                    0.9    275 1.0  0.8 7.0  11.5                          36.5                              0.4                                 41.7                                    2.2    275 0.5  0.5 4.0  7.6 54.5                              0.2                                 30.1                                    3.1    300 0.5  0.6 5.5  9.2 51.8                              0.1                                 27.2                                    5.6    300 1.0  1.2 13.0 22.3                          18.2                              0.4                                 43.0                                    1.9    __________________________________________________________________________

Others include C₆ F₁₂ Cl₂.

Example 17 Reaction of F112a and Hydrogen Catalyst: 2% Ru/YF₃, 16.5 g 10mL

The H₂ :F112a molar ratio was varied between 0.5:1 and 1:1 and thecontact time was 20 seconds. Results in area % at various temperaturesare shown in the table.

    __________________________________________________________________________    Temp.        Ratio    ° C.        H.sub.2 :112a            F1112a                F122                   C.sub.4 F.sub.4 Cl.sub.2                       C.sub.4 F.sub.4 Cl.sub.2                           F112a                               F1314                                   F1314                                       Others    __________________________________________________________________________    175 1.0 12.1                3.8                   0.6 0.0 72.5                               8.7 2.0 0.3    200 1.0 20.7                7.5                   1.6 0.0 52.1                               13.6                                   3.5 1.1    250 1.0 35.5                15.6                   6.1 0.1 18.8                               16.1                                   5.0 2.8    250 0.5 27.4                15.2                   2.6 0.1 35.8                               12.7                                   3.8 2.6    300 0.5 39.1                11.9                   2.2 0.3 31.0                               9.5 3.2 2.8    300 1.0 57.2                14.9                   9.7 1.2 3.8 6.6 2.6 4.1    __________________________________________________________________________

Example 18 Reaction of F114a and Hydrogen Catalyst: 2% Ru/YF₃, 16.5 g,10 mL

The H₂ :F114a molar ratio was 2:1, the temperature was 350° C. and thecontact time was 20 seconds. The products in area % were CH₄, 5.4,F143a, 4.1; F134a, 0.6; F124, 31.0; F1318, 3.0; F114a, 29.6; F1318, 3.0;F1112a, 1.7; F318, 3.4; F318, 3.9 C₆ Cl₂ F₁₀, 1.5; and others, 9.0.

Example 19 Reaction of F113a and Hydrogen Catalyst: 2%Ru/SmF₃, 20.6 g,10 mL

The H₂ :F113a molar ratio was 1 and the contact time was 20 seconds.Results in area % at 175° C. showed the presence of the followingcompounds: F143a, 3.8; F142b, 0.4; F123, 4.6; F113, 0.4; F113a, 24.6;t-F1316, 43.8; c-F1316, 21.7 and 1.0 others. Others include C₂ H₆, F133aand F114a.

Example 20 Reaction of F216aa and Hydrogen Catalyst: 2% Ru/SmF₃, 20.6 g,10 mL

The H₂ :F216aa molar ratio was varied between 0.5:1 and 2:1 and thecontact time was 20 seconds. Results in area % at various temperaturesare shown in the table.

    __________________________________________________________________________    Temp.        Ratio    ° C.        H.sub.2 :F216aa             HFP                F236fa                    F1215xc                         F226da                             F216aa                                 C.sub.6 F.sub.12                                    Others    __________________________________________________________________________    200 1.0  1.0 5.4                    4.3  6.2 64.9                                 16.1                                    2.1    200 2.0  1.1 11.3                    9.9  10.1                             46.1                                 19.2                                    2.4    225 2.0  1.0 14.4                    16.9 16.1                             22.2                                 25.8                                    3.8    225 1.0  0.9 9.1                    13.1 12.1                             37.6                                 24.2                                    3.0    250 1.0  1.0 6.2                    19.4 16.9                             24.6                                 28.1                                    3.8    250 2.0  1.0 13.9                    26.4 20.6                             1.2 31.2                                    5.7    250 0.5  0.9 1.8                    9.1  7.8 55.2                                 23.1                                    2.2    __________________________________________________________________________

Others include CH₄, C₂ H₆, C₃ H₈, F1224, C₆ HF₁₁, C₅ F₉ Cl, F1223,F1214, C₆ F₁₀, F1225zc and C₆ F₁₃ Cl.

Example 21 Fluorination of F113a Catalyst: 2% Ru/SmF₃, 20.6 g, 10 mL

The HF:F113a molar ratio was 2:1 and the contact time was 20 seconds.Results in mole % at various temperatures are shown in the table.

    ______________________________________    Temp. ° C.             F13    F115    F114a F113  F113a Others    ______________________________________    250      0.0    0.0     1.1   0.3   98.5  0.1    275      0.0    0.0     3.0   0.3   96.4  0.3    325      0.3    0.0     14.4  0.3   84.7  0.3    350      0.3    0.1     22.1  0.3   77.0  0.2    ______________________________________

Example 22 Reaction of F216aa and Hydrogen Catalyst: 2% Ru/EuF₃, 19.1 g,10 mL

The H₂ :F216aa molar ratio was varied between 0.5:1 and 1:1 and thecontact time was 20 seconds. Results in area % at various temperaturesare shown in the table.

    __________________________________________________________________________    Temp.        Ratio    ° C.        H.sub.2 :F216aa             F236fa                 F1215xc                      F226da                          F216aa                              C.sub.6 F.sub.10                                 F151-12mmtt                                        Others    __________________________________________________________________________    175 1.0  2.4 21.2 5.5 60.8                              2.3                                 7.3    0.7    176 0.5  1.2 12.4 3.2 74.9                              1.7                                 6.1    0.4    200 0.5  1.0 7.5  3.4 72.8                              0.8                                 14.2   0.4    __________________________________________________________________________

Others include F1225zc, F1214, and C₆ HF₁₁.

Example 23 Reaction of F113a and Hydrogen Catalyst: 2% Ru/EuF₃, 19.1 g,10 mL

The H₂ :F113a molar ratio was 1 and the contact time was 20 seconds.Results in area % at 175° C. showed the presence of the followingcompounds: F143a, 2.0; F114a, 0.3; F123, 6.9; F113, 0.3; F113a, 22.0;t-F1316, 44.7; c-F1316, 23.0 and 0.7 others. Others include F1132a,F142b, F133a and F1112a.

Example 24 Fluorination of F113a Catalyst: 2% Ru/EuF₃, 19.1 g, 10 mL

The HF:F113a molar ratio was 2:1 and the contact time was 20 seconds.Results in mole % at various temperatures are shown in the table.

    __________________________________________________________________________    Temp. ° C.          F115             F114a                 F123                    F113                       F113a                           t-F1326                               C-F1326                                    Others    __________________________________________________________________________    200   0.0             0.3 0.1                    0.3                       98.3                           0.6 0.4  0.1    250   0.0             0.4 0.1                    0.3                       98.1                           0.6 0.4  0.1    300   0.0             1.0 0.0                    0.3                       97.6                           0.5 0.4  0.1    350   0.1             6.5 0.0                    0.3                       92.1                           0.5 0.4  0.1    __________________________________________________________________________

Example 25 Reaction of F113a and Hydrogen Catalyst: 2% Ru/DyF₃, 21.1 g,10 mL

The H₂ :F113a molar ratio was 1 and the contact time was 20 seconds.Results in area % at 175° C. showed the presence of the followingcompounds: F143a, 2.3; F114a, 0.3; F123, 6.9; F113, 0.3; F113a, 27.5;t-F1316, 42.6; c-F1316, 19.9 and 0.4 others. Others include F1132a,F142b, F133a and F1112a.

Example 26 Reaction of F216aa and Hydrogen Catalyst: 2% Ru/DyF₃, 21.1 g,10 mL

The H₂ :F216aa molar ratio was varied between 0.5:1 and 1:1 and thecontact time was 20 seconds. Results in area % at various temperaturesare shown in the table.

    __________________________________________________________________________    Temp.        Ratio    ° C.        H.sub.2 :F216aa             F236fa                 F1215xc                      F226da                          F216aa                              C.sub.6 F.sub.10                                 F151-12mmtt                                        Others    __________________________________________________________________________    175 1.0  1.5 7.2  1.8 79.0                              0.7                                 7.7    2.1    200 0.5  1.4 10.2 2.3 72.1                              0.8                                 11.1   2.1    250 1.0  4.8 23.8 9.3 28.6                              1.1                                 29.4   3.1    __________________________________________________________________________

Example 27 Fluorination of F113a Catalyst: 2% Ru/DyF₃, 21.1 g, 10 mL

The HF:F113a molar ratio was 2:1 and the contact time was 20 seconds.Results in mole % at various temperatures are shown in the table.

    ______________________________________    Temp. ° C.            F114a   F113   F113a F1326  F1326 Others    ______________________________________    300     1.5     0.3    97.8  0.1    0.1   0.2    350     9.0     0.3    90.1  0.2    0.1   0.2    ______________________________________

Catalyst Comparisons Reaction of F216aa and Hydrogen

The table below, compares the performance of selected catalysts reportedin the Examples above for the conversion of F216aa to F151-12mmtt at anoperating temperature of 200° C., H₂ /F216aa ratio of 0.5 and a contacttime of 20 seconds. The data is from examples cited and the results arereported in area %. In this table, Catalyst 1 is 5% Ru on fluoridedalumina, Catalyst 2 is 2% Ru on aluminum fluoride, Catalyst 3 is 2% Ruon dysprosium fluoride and Catalyst 4 is 2% Ru on europium fluoride.

    ______________________________________    Catalyst          F236fa   F1215xc  F226da F216aa                                         F151-12mmtt    ______________________________________    1     2.2      0.7      8.5    76,3  10.8    2     3.3      3.1      4.3    74.7  13.4    3     1.4      10.2     2.3    72.1  11.1    4     1.0      7.5      3.4    72.8  14.2    ______________________________________

Catalyst Comparisons Reaction of F216aa and Hydrogen

The following table compares selected data reported in the Examplesabove for the conversion of F216aa to F151-12mmtt, F1215xc and F226da atan operating temperature of 200° C., contact time of 20 seconds, and H₂/F216aa molar ratio of 1. In this table, Catalyst 1 is 2% Ru onmagnesium fluoride, Catalyst 2 is 2% Ru on calcium fluoride and Catalyst3 is 2% Ru on barium fluoride. Results are in area %.

    ______________________________________    Catalyst          F236fa   F1215xc  F226da F216aa                                         F151-12mmtt    ______________________________________    1     0.2      20.9     4.4    62.2  8.1    2     1.8      1.3      2.6    77.5  16.3    3     0.6      40.0     33.3   23.7  1.3    ______________________________________

Catalyst Comparisons Reaction of F113a and Hydrogen

The following table compares selected data from the Examples above onthe reaction of F113a and hydrogen over various catalysts. In thistable, all the supports had 2% ruthenium by weight. Reactor temperaturewas 175° C., contact time 20 seconds and the H₂ /F113a ratio was 1.Results are in area %.

    ______________________________________    Support           F143a   F123    F113a t-F1316                                        c-F1316                                              Others    ______________________________________    SmF.sub.3           3.9     4.4     25.1  43.5   21.6  1.5    EuF3   1.9     6.7     22.6  44.3   23.2  1.3    DyF.sub.3           2.2     6.7     28.4  42.1   19.4  1.2    ______________________________________

Others include F1132a, F142b, F133a, F112a and F114a.

I claim:
 1. A process for decreasing the chlorine to carbon ratio for saturated or olefinic halogenated hydrocarbons containing chlorine and having the formula C_(k) H_(g) Cl_(h) F_(i) where k is an integer from 1 to 6, g is an integer from 0 to 4, h is an integer from 1 to 13, and i is an integer from 0 to 13, in the presence of a catalyst, characterized by:(a) employing a catalyst comprising ruthenium supported on a fluoride of at least one element selected from the group consisting of Zn, Mg, Ba, Y, Sm, Eu, and Dy; and (b) increasing the fluorine content of said halogenated hydrocarbons by reacting them with HF in the vapor phase.
 2. The process of claim 1 wherein the catalyst consists essentially of ruthenium supported on zinc fluoride.
 3. The process of claim 1 wherein the catalyst consists essentially of ruthenium supported on a fluoride of at least one element selected from the group consisting of Y, Sm, Eu and Dy.
 4. The process of claim 1 wherein the catalyst comprises ruthenium supported on a calcium-magnesium fluoride where the atomic ratio of calcium to magnesium is between about 1:1 and 4:1.
 5. The process of claim 1 wherein the catalyst comprises ruthenium supported on a calcium-barium fluoride where the atomic ratio of calcium to barium is between about 1:1 and 4:1.
 6. A process for decreasing the chlorine to carbon ratio for a halogenated hydrocarbon containing two chlorine substituents on the same carbon atom and having the formula C_(n) H_(a) Cl_(b) F_(c) where n is an integer from 1 to 4, a is an integer from 0 to 1, b is an integer from 2 to 9, c is an integer from 0 to 9, and a+b+c equals 2n+2, in the presence of a catalyst, characterized by:(a) employing a catalyst comprising ruthenium on a support selected from the group consisting of (1) fluorided alumina, (ii) aluminum fluoride, and (iii) fluorides of at least one metal selected from the group consisting of Zn, Mg, Ca, Ba, Y, Sm, Eu, and Dy; and (b) reacting said halogenated hydrocarbon in the vapor phase to remove two chlorine substituents from the same carbon atom of said halogenated hydrocarbon and to produce a dimerized olefin of the formula C_(2n) H_(2a) Cl_(2b-4) F_(2c).
 7. A process for decreasing the chlorine to carbon ratio for halogenated hydrocarbons containing chlorine and having the formula C_(m) H_(d) Cl_(e) F_(f) where m is an integer from 2 to 6, d is an integer from 0 to 2, e is an integer from 2 to 4, f is an integer from 3 to 12, and d+e+f equals 2m+2, in the presence of a catalyst, characterized by:dehalogenating said halogenated hydrocarbons in the presence of a catalyst comprising ruthenium on a support selected from the group consisting of (i) fluorided alumina, (ii) aluminum fluoride, and (iii) fluorides of at least one metal selected from the group consisting of Zn, Mg,,Ca, Ba, Y, Sm, Eu, and Dy, by reacting said compound with hydrogen in the vapor phase to produce an olefin of the formula C_(m) H_(d) Cl_(e-y) F_(f-y), where y is an integer from 1 to 2 when m is an integer from 2 to 3, and y is an integer from 2 to 4 when m is an integer from 4 to 6, provided that a chlorine atom on each of two adjacent carbons or a fluorine and a chlorine atom on two adjacent carbons, but not a fluorine atom on each of two adjacent carbons, are removed.
 8. The process of claim 7 wherein CF₃ CCl₂ CF₃ is reacted with hydrogen to produce CF₃ CCl═CF₂. 